Scribing film



United States Patent 3,416,926 SCRIBING FILM Albert C. Smith, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Oct. 2, 1964, Ser. No. 401,235 Claims. (Cl. 96-94) ABSTRACT OF THE DISCLOSURE A scribing film of a type comprising a plate support having a gelatin layer thereover, wherein said gelatin layer has incorporated therein a dispersion containing a substantially pure and substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., which material has a plasticizing efiect on the gelatin.

This invention relates to improved light-sensitive and non-light-sensitive scribing films.

In certain applications, such as map making and optical gauging, very uniform and accurate lines are required. A convenient method for preparing such lines is to employ a sharp instrument to scribe a line in a suitable opaque layer coated on a transparent support. The scribing technique is also useful in graphic arts where densities are locally reduced by scraping or scribing away upper film layers until the desired density is obtained.

Scribing films have been provided which feature a gelatin coating containing dye, pigment or a high contrast silver halide emulsion. Although these scribing films are useful, it is desirable to provide an improvement therein whereby the edges of lines scribed thereon are more even and in which areas where the lines intersect remain open.

One object of this invention is to provide improved scribing films. Another object of this invention is to provide scribing films in which the edges of scribed lines remain very even and the areas where scribed lines intersect remain open. A further object of this invention is to provide improved light-sensitive scribing films. Other objects of the invention will appear herein.

These and other objects of the invention are accomplished by proving scribing films which feature a gelatin layer having dispersed therein a substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., said organic material having a plasticizing effect on the gelatin. Advantageously, the dispersed crystalloidal material is substantially free from dissolved addenda, such as developer, ultra-violet inhibitors, color formers, e.g., photographic couplers, or dye developers.

In one embodiment of the invention, scribing films are provided having a support transparent to certain radiation, and a gelatin coating thereover containing (1) a substance which is opaque to said radiation, and (2) an organic material of the type described above.

In another embodiment of the invention, light-sensitive scribing films are provided comprising a support having coated thereon a high-contrast silver halide emulsion containing an organic material of the type described above.

It has been found that scribing films in accordance with the invention demonstrate a substantial improvement over those of the prior art with respect to the highly even quality of the edges of lines scribed thereon, and with respect to the fact that the areas where scribed lines intersect remain open.

This invention will be further illustrated in the following examples. Example 1 demonstrates a non-light-sensitive film in accordance with the invention.

Ice

Example 1 To 4300 cm. of a heated (40 C.) dispersion of lead chromate in gelatin containing approximately 1 mole of lead chromate, Rose Bengal to provide an orange hue and 10 grams of gelatin were added 300 gm. of a 10% aqueous solution of bone gelatin, 200 cc. of a 15.3% aqueous solution of saponin, 104 cc. of a 2.7% aqueous solution of mucochloric acid (hardener) and 140 gm. of a second dispersion of di-n-butyl phthalate, and distilled water to make 5.05 kg. total weight. The second dispersion was prepared by melting 400 gm. of an aqueous 10% solution of bone gelatin at 40 C., adding 60 cc. of a 5% aqueous solution of Alkanol B (alkylnaphthalene sodium sulfonate wetting agent) and stirring into the mixture 400 gm. di-nbutylphthalate. The dispersion was passed through a colloid mill five times, and then chill set.

A scribing plate was prepared by coating this mixture on a clear glass support at the rate of about 630 mg./ ft. lead chromate, 430 mg./ft. gelatin and 120 mg./ft. di-n-butylphthalate. Upon drying, lines were scribed on the film. The edges of the lines exhibited very good evenness and areas where the lines intersected remained open.

A light-sensitive scribing film in accordance with the invention is described in Example 2.

Example 2 A high contrast silver chlorobromide emulsion was prepared which contained more than 60 percent silver chloride, a coating aid, spectral and chemical sensitizers, antifoggant and hardener, together with grams per mole of silver of the di-n-butylphthalate dispersion prepared as described in Example 1. The emulsion was coated on glass to give a coverage of 476 mg. silver, 500 mg. gelatin, and 144 mg. di-n-butylphthalate per square foot. The sensitometric properties of the film were tested and showed no adverse effects due to the addition of di-n-butylphthalate dispersion. The scribing properties of the film were distinctly superior to a control prepared in the same manner except that di-n-butylphthalate was not incorporated in the emulsion.

The highly unexpected nature of my invention will be demonstrated in Example 3. A first film support was coated with a mixture of gelatin containing a dispersion of black colloidal silver (257 grams), an aqueous 2.7% solution of mucochloric acid (1.9 cc.), a 50% aqueous solution of glycerine (6 cc.) and a 15% aqueous saponin solution (1.5 cc.). A second film support was coated with a dispersion of black colloidal silver gm.), a 2.7% aqueous solution mucochloric acid (0.6 cc.), a 15 aqueous saponin solution (5 cc.), distilled water (6 cc.) and 9.2 grams of the di-n-butylphthalate dispersion prepared as described in Example 1.

Crossed lines were scribed on the two coatings thus pre pared with a sharp scribing tool. Photomicrographs (20X) were taken of the samples. The edges of the lines scribed on the sample which did not contain the di-nbutylphthalate dispersion were ragged and uneven, and the lines scribed thereon remained closed at the point of intersection (i.e., the edges of the second line were visible even where it crossed the first line). However, the sample in which the di-n-butylphthalate dispersion was incorporated had lines which were very even along the edges and the area where the lines intersected remained open (the edges the second line were not visible where it crossed the first line).

It has been found that a large number of compounds may be advantageously incorporated in the gelatin layer of scribing films to provide the substantial improvements realized with di-n-butylphthalate. Typical useful highboiling crystalloidal materials include the following:

Acids p-sec. Amylbenzoic acid fl-Phenylpropionic acid Dibenzyl acetic acid Phenyl ethyl acetic acid Mono-n-amylphthalate (acid ester) Undecylenic acid Benzyl hydrogen succinate (acid ester) Alcohols n-Hexylphenylcarbinol fi-(p-tert. Butyl phenoxy) -ethyl alcohol Amides Acetyl n-butyl aniline Acetyl methyl p-toluidine Benzoyl piperidine Amide derivatives N-n-arnylphthalimide N-n-amyl succinimide N-Z-cyanobutylphthalimide Carbamates Ethyl N,N-di-n-butyl carbamate Ethyl N-phenyl carbamate Esters Ketone derivatives Benzophenone 2,4'-dichlorobenzophenone a-Methoxy acetophenone Acetophenone 2,4-dihydroxy valerophenone p-Sec.-amylbenzophenone Phenol ethers Veratrole (1,2-dimethoxybenzene) Eugenol methyl ether Hydroquinone dimethyl ether Phosphate esters Triphenyl phosphate Tricresyl phosphate Diphenyl mono-p-tert. butyl phenyl phosphate Monophenyl di-p-tert. butyl phenyl phosphate Diphenyl mono-o-chloro-phenyl phosphate Monophenyl di-o-chlorophenyl phosphate Tri-p-tert. butyl phenyl phosphate Tri-o-phenylphenyl phosphate 4 Di-p-tert. butyl phenyl mono (S-tert. butyl-2-phenyl) phenyl phosphate Sulfonamides p-Toluenesulfonyl methyl o-toluidine p-Toluenesulfonyl dimethylamide Sulfonamide derivatives p,p-di-n-Amylbenzenesulfonanilide p-Toluenesulfonyl di-n-butyl amide Sulfones n-Bntyl sulfone Iso-amyl sulfone Ureas N,N'-diethyl-N,N-diphenyl urea N,N-di-n-butyl urea The high-boiling materials described above may be incorporated in the gelatin in any convenient manner. Preferably, the materials are added to a heated solution of gelatin containing a suitable wetting agent. Suitable wetting agents include sodium diisopropylnaphthalene sulfonate, sodium lauryl sulfonate, p-tert.-octylphenoxy diethoxy sulfonate sodium salt, sodium N-methyl-N-oleoyl taurate (diisobutylcresoxyethoxyethyl) dimethyl-benzylammonium chloride (diisobutylphenoxyethoxyethyl) dimethyl-benzylamrnonium chloride and the like.

The most useful concentration of the high-boiling crystalloidal materials in the scribing layers is from 4 to 100%, based on the weight of the gelatin. Advantageously, the dispersion of crystalloidal material in the gelatin coating is in the form of finely-divided droplets, the droplets preferably being less than about 10 microns in size, such as from .5 to 5 microns. As noted above, it is desirable that the crystalloidal material be substantially free from any dissolved addenda.

The non-light-sensitive scribing films of the invention are advantageously coated on a transparent support; preferably glass. The gelatin layer in these scribing films contains a colored compound, such as a dye or pigment, to prevent passage of visible light. Typical useful pigments include cadmium sulfide, cadmium selenide, lead oxide yellow, red lead, lead chromate, carbon black, lead chocolate, Prussian blue, chrome oxide green and chrome red. Illustrative dyes which may be employed include Rose bengal, methyl violet, Eriochrome black, brilliant fast blue, benzo fast yellow, Immedial green and para red. If desired, combinations of suitable dyes and pigments may be used.

The photosensitive scribing films of the invention are high-contrast emulsions including those which contain from 60 to 100% silver chloride. Advantageously, the emulsions employed in my invention contain from 70 to 92% silver chloride, from 8 to 30 mole percent silver bromide and up to 5 mole percent silver iodide (it being understood that these emulsions always contain at least 60 mole percent silver chloride). I may also use, in accordance with the invention, the emulsions described in US. Patent 2,756,148 (1956) of Mac- William, which emulsions contain from 40 to mole percent silver chloride and from 10 to 60 mole percent bromide, which emulsions are prepared by initially precipitating a relatively chloride-rich precipitate which is subsequently converted to a bromide-enriched silver chlorobromide by the addition of bromide ions during at least the last Vs of the precipitation cycle of the emulsion making procedure. Advantageously, the silver chlorobromide is precipitated at a higher temperature (50 C. to 95 C.) than normally is used.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A scribing film having a plate support transparent to certain visible light radiation, and a gelatin layer coated thereon, wherein said gelatin layer contains (1) a substance which renders the gelatin layer opaque to visible light radiation, and (2) a dispersion containing a substantially pure and substantially Water-insoluble, 10W molecular weight, organic, crystalloidal material having a boiling point above about 175 C., which material has a plasticizing effect on the gelatin.

2. A photographic scribing film comprising a transparent plate support having coated thereon a gelatin layer of silver halide emulsion selected from the group consisting of silver halide emulsions containing 60 to 100 mole percent chloride, to 40 mole percent bromide and 0 to mole percent iodide, and silver halide emulsions containing from 40 to 90 mole percent chloride and from to 60 mole percent bromide prepared by first precipitating a relatively chloride rich silver halide precipitate and converting the precipitate to a bromide enriched silver chlorobromide emulsion by the addition of bromide ions, said emulsion having incorporated therein a dispersion of a substantially pure and substantially Water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., which material has a plasticizing effect on the gelatin.

3. A scribing plate comprising a transparent glass support having a gelatin layer coated thereon, said gelatin layer containing (1) lead chromate in a concentration sutficient to effectively prevent passage of light through the gelatin layer, and (2) 4 to 100%, based on the weight of the gelatin, of a dispersion containing substantially pure di-n-butylphthalate, said di-n-butylphthalate being in the form of droplets from .5 to 10 microns in size.

4. In a method of manufacturing a scribing film of a type comprising a transparent plate support having coated there-on a gelatin layer, the improvement which comprises the steps of incorporating in the gelatin layer a dispersion containing a substantially pure and substantially Water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., and then scribing said film.

5. In a method of manufacturing a photographic scribing film comprising a transparent plate support having coated thereon a gelatin layer of a silver halide emulsion selected from the group consisting of silver halide emulsion containing to mole percent chloride, 0 to 40 mole percent bromide and 0 to 5 mole percent iodide, and silver halide emulsions containing from 40 to 90 mole percent chloride and from 10 to 60 mole percent bromide prepared by first precipitating a relatively chloride rich silver halide precipitate and converting the precipitate to a bromide enriched silver chlorobromide emulsion by the addition of bromide ions, the steps of incorporating in said emulsion a dispersion containing a substantially pure and substantially water-insoluble, low molecular weight, organic crystalloidal material having a boiling point above about C. and then scribing said film,

References Cited UNITED STATES PATENTS 2,454,043 11/1948 Dimsdale et al. 96109 2,969,731 1/1961 Kendall 9648 3,033,680 5/1962 Milton et al. 96109 3,042,524 7/1962 Albus et al. 96109 3,244,519 4/1966 Schwerin 96115 2,322,027 6/1943 Jelley et al. 96'74 2,852,381 9/1958 Minsk et al 96100 2,980,534 4/1961 Printy et al 9693 3,170,791 2/1965 Cunningham 9693 OTHER REFERENCES The Merck Index, 1952, pp. 566-7, AS356.M529.

NORMAN G. TORCHIN, Primary Examiner.

C. E. DAVIS, Assistant Examiner.

US. Cl. X.R. 

